Isodibenzanthrone-selenazole and process of preparing the same



herewith. V This invention relates to selenium compounds Patented July 23, 1935 UNITED STATES ISOD I 'BENZANTHR ON'ESELENAZOLE AND;

PROCESS-OF PREPARING THE SAlVIE Alexander J. Wuertz,'Carrollville, and Myron "S.

Whelen; Milwaukee, -Wis., assignrs to E. 'I.du

Pont de Nemours & Company, .Wilmington, Del., a corporation of Delaware v y No Drawing. Original application April 29, 1933, Serial No; 668,623. Divided and this applica tion April 29, 1933, Serial No. 668,624 l i 16Claims. (Cl. 260- 14)] j This application adivision of our copending application Ser. No. 668,623, filed of even date of the isodibenzanthrone series; It is an object of this invention to iprepare novel compounds of the isodibenzanthrone series which are useful as vatdyestuffs. Other and further important objects of this invention will appear as the "description proceeds. V v d j The compounds with which this invention deals are characterized by possessing in their structure an isodibenzanthrone nucleus which is substituted by both selenium and nitrogen. Thelatter two elements are very probably presentin the form of a selenazole ring. With due allowance for partial decomposition of the selenazole' ring during the fusion process by which our novel compounds are formed, they. probably constitute mixtures of isodibenzanthrone-diselenazoles and isodibenzanthrone-monoselenazoles." v

The products of this invention are navy blue to dark blue vat dyestuffsdepending on the particular substituent in'the'carbon atom of the selenazole ring, aswell as on the presence, or absence of substituents, such as halogen, in the isoolibenzanthrone nucleus. They are prepared by caustic fusion of the B zl-halogen-benzanethroneeselenazoles described and claimed in our copending application of even date, Ser. No. 668,621, wherein the Bzl-halogen-benzanthroneselenazoles are prepared by reducing an anthraquinone l -2eselenazole in sulfuric acid and either simultaneously or subsequently condensing it with glycerine. ..The benzanthrone-selenazole so produced may have the structure corresponding to one'of the following formulae:

product is not a mixture of the three or any two 7 of them.

The benzanthrone-selenazole product is then halogenated by suspendingit in water'and treating the suspension with a halogenating agent- .The caustic fusion maybecarried out along analogous lines with the knowniproceduresfor fusing Bzl-halogen-benzanthrones to isodibenzanthrones. See, for instance, U! SI Patent No.

906,367 1 The preferred' method' involves the use of alcohol as a diluent and employs a temperature between and 170 C. "It is advantageous, however, to adhere to the lowertemperaturesystiy to"140 C., in order to minimizedecompos'i tion of the selenazole ring. a

/ Isodibenzanthrones substituted' in meanness may be obtained by'fusing correspondingly substituted-Bz1 halogen -'-benZanthrone-selenazoles,

or the unsubstituted -'isodibenzanthrone;selen}- azoles may be formed first and thensubjectedto an operation for introducing'substituents,\as wil1 be readily understoodvby those skilled in the art.

Without limiting our invention to any particuparts mentioned are by weight A 7 Example 1-.Fusion of Bzl-brom benzanthrone 1,2-phenyZ-selenaeole to illustrate ou specific mode of ,operation'f; The

Paris of sddiufil dissolvejdjin z'opartsfd alcohol, and thereto are added 20 partsof potasluted with about; parts of: water,

,w h dir eo im r e with? t t q i l ea lar fprocedure; the followingexample's are gjiven I Example 2.--Fusion of B21 -chZor-benzanthrone- Lz-phenyl-selenazole 'Iparts of sodium are dissolved in 50 parts of alcohol, and thereto are added 50 parts-of potassium hydroxide. The melt is heated to 125* C.

and maintained at this temperature until completely fluid. 10 parts of Bzl-chlor-benzanthrone- 1,2-phenyl-selenazole (Example 7 of copending' application, Ser. No. 668,621), are then added and the reaction mass is heated at about 135 C. for one hour. The isodibenzanthrone-selenazole body so formed isisolated as in Example 1, and appears to be identical with the product therein obtained.

Example 3.-Chlorination of selenazole subst'ituted isodibenzanthrone 10 parts of phenyl-selenazole-isodibenzanthrone (as obtained according to Example 1 above) are suspended in 100'parts of ortho-dichloro-benzene, and chlorine gas is slowly passed into the mixture until a. chlorine content of about two atoms of chlorine has been reached. The halogenated dyestufi is then filtered off, and washed successively with ortho-dichloro-benzene and alcohol. his a navy blue powder, which dyes cotton from a greenish-blue vat in navy blue shades. Dyeings so'made are of superior iastness to water than those of dichloro-isodibenzanthrone.

Example 4.--Bromination of phenyl-selena-zoleisodwenzanthrmie 10 parts of phenyL-selenazole-isodibenzanthrone (prepared according to Example 1 above) are dissolved in 100'parts of chlorosulfonic acid. A trace of iodine is added, and then 5 parts of liquid bromine are introduced over a short period of time. The whole is then stirred until evolution of hydrobromic acid has practically ceased. The dyestuff is isolated by pouring the chlorosulfonic acid solution onto ic'e, followed by filtration and washing. The product so obtained is a violet powder which dyes cotton from a greenish-blue vat in navy blue shades of good fastness to water spotting. It corresponds in bromine content to a dibr'omo compound. a Etmmple 5.'Chlo rination of phenyl-selenaeoleisodibenzanthrone 10 parts of phenyl-selenazole-isodibenzanthrone are dissolved in 100 parts of chlorosulfonic acid. A trace of iodine is added, and chlorine gas is then passed in slowly until the evolution of hydrochloric acid has practically ceased. The chlorinated body thus formed is isolated in a manner analogous to that shown in Examples 3 and 4. It

dyes cotton from a greenish-blue vat in navy blue shades, which are reasonably fast against water spotting. Its chlorine content corresponds to a dichloro compound.

It will be understood that many variations and incdifi ations are possible in our preferred mode of operation without departing from: the spirit of this invention. I

In the claims below it should be understood that where new products, dyestuffs, or articles of manufacture are claimed, we mean to include these bodies not only in substance, but also in whatever state they exist when applied to material dyed, printed, or pigmented therewith.

We claim: A r v 1. A selenium containing vat dyestuff of the isodibenzanthrone series, yielding upon cotton navy blue to dark blue dyeings of superior waterfastness than those of isodibenzanthrone, said dyestuif being obtainable by subjecting to alkali fusion a Bzl-halogen-benzanthrone-1,2-selenazole in which the beta position in the anthraquinone nucleus' adjacent the Bz-ring is unsubstituted.

2. A vat dyestufi comprising chiefly an isodibenzanthrone-alpha,beta-selenazole.

3."A- vat d'yestufi comprised chiefly of isodibenzanthrone C-C-diphenyl alpha,beta-alpha, beta'-diselenazole.

4. The process of producing a vat clyestuff of the isodibenzanthrone series which comprises subjecting to alkali fusion a Bzl-halogen-benzanthrone-alpha,beta-selenazole in which the beta position in the anthraquinone nucleus adjacent the Bz-ring is unsubstituted.

5. The process of producing a vat dyestufi of the isodibenzanthrone series which comprises subjecting to alkali fusion a Bzl-halogen-benzanthroiie C phenyl alpha,beta selenazole in which the beta position in the anthraquinone nucleus adjacent the Bz-ring is unsubstituted.

6. The process of producing a vat dyestufi of theisodibenzanthrone series which comprises fusing a Bzl halogen-benzanthrone-1,2-se1enazole in which the beta position in the anthraquinone nucleus adjacent the Bz-ring is unsubstituted with alcoholic caustic alkali at a temperature between 120 and 140 C. I

7. The process of producing a vat dyestuf'f of the isodibenzanthrone series which comprises fusing Bzl-halogen-benzahthrone 1,2-C-phenylselenazole with alcoholic caustic alkali at a temperature between 120 and 140 C.

8. The process of producing a vat dyestuff of the isodibenzanthrone series which comprises fusing a Bzl-halogen-benzanthrone-1,2-selenazole in which the beta position in the anthraquinone nucleus adjacent the Bz-ring is unsubstituted with alcoholic caustic alkali at a temperature between 120 and 140 C., and subjecting the product to halogenation.

9; The process of producing a vat dyestuff. of the 'isodibenzanthrone series which comprises fusing Bzl-halogen-benzanthrone-1,2-C-phenylselenazole with alcoholic caustic alkali at a temperature between 120 and 140 C., and subjecting. the product to halogenation."

10. The process of producing a vat dyestufi of the isodibenzanthronc series, which comprises chlorinating an isodibenzanthrone-C-phenylalpha, beta-selenazole in an'inert organic suspending medium.

- 11'.The process of producing a vat dyestuifi of the isodibenzanthrone series which comprises chlorinating an isodibenzanthrone-C-phenylalpha,beta-selenazole in chlorosulfonic acid.

121. The process of producing a vat dyestuif of the isodibenzanthrone' series which comprises brominating an isodibenzanthrone-C-phenylalpha,beta-selenazole in chlorosulfonic acid.

13. The process of producing a vat dyestuif of the is'odibenzanthrone series, which comprises halogenating an isodibenzanthrone-C-pheny1- alpha,betaselenazole in an inert suspending medium and. in the presence of a. halogenaticm 16. Dibrominated isodibenzanthrone-C-phecatalyst. nyl-alpha,beta,-se1enazo1es.

14. Halogenated isodibenzanthrone-C-phenylalphabeta-selenazoles. ALEXANDER J. WUERIZ. 5 15. Dichlorinated v isodibenzanthrone-C-phe- N MYRON S, WHELEN.

ny1-a1pha,beta se1enazoles. 

